HC⋮P and H3C−C⋮P as Proton Acceptors in Protonated Complexes Containing Two Phosphorus Bases:  Structures, Binding Energies, and Spin−Spin Coupling Constants

2007 ◽  
Vol 111 (39) ◽  
pp. 9924-9930 ◽  
Author(s):  
Ibon Alkorta ◽  
José Elguero ◽  
Janet E. Del Bene
Keyword(s):  
Binding Energies ◽  
Coupling Constants ◽  
Spin Coupling ◽  
Spin Coupling Constants ◽  
Spin Spin Coupling ◽  
Protonated Complexes

Using one halogen bond to change the nature of a second bond in ternary complexes with P⋯Cl and F⋯Cl halogen bonds

2017 ◽  
Vol 203 ◽  
pp. 29-45 ◽  
Author(s):  
Janet E. Del Bene ◽  
Ibon Alkorta ◽  
José Elguero
Keyword(s):  
Halogen Bond ◽  
Synergistic Effects ◽  
Ternary Complexes ◽  
Binding Energies ◽  
Coupling Constants ◽  
Spin Coupling ◽  
Halogen Bonds ◽  
Binary Complexes ◽  
Spin Coupling Constants ◽  
Spin Spin Coupling

Ab initio MP2/aug’-cc-pVTZ calculations have been carried out to determine the effect of the presence of one halogen bond on the nature of the other in ternary complexes H2XP:ClF:ClH and H2XP:ClF:ClF, for X = F, Cl, H, NC, and CN. The P⋯Cl bonds remain chlorine-shared halogen bonds in the ternary complexes H2XP:ClF:ClH, although the degree of chlorine sharing increases relative to the corresponding binary complexes. The F⋯Cl bonds in the ternary complexes remain traditional halogen bonds. The binding energies of the complexes H2XP:ClF:ClH increase relative to the corresponding binary complexes, and nonadditivities of binding energies are synergistic. In contrast, the presence of two halogen bonds in the ternary complexes H2XP:ClF:ClF has a dramatic effect on the nature of these bonds in the four most strongly bound complexes. In these, chlorine transfer occurs across the P⋯Cl halogen bond to produce complexes represented as (H2XP–Cl)+:−(F:ClF). In the ion-pair, the cation is also halogen bonded to the anion by a Cl⋯F− halogen bond, while the anion is stabilized by an −F⋯Cl halogen bond. The central ClF molecule no longer exists as a molecule. The binding energies of the ternary H2XP:ClF:ClF complexes are significantly greater than the binding energies of the H2XP:ClF:ClH complexes, and nonadditivities exhibit large synergistic effects. The Wiberg bond indexes for the complexes H2XP:ClF, H2XP:ClF:ClH, and H2XP:ClF:ClF, and the cations (H2XP–Cl)+ reflect the changes in the P–Cl and Cl–F bonds. Similarly, EOM-CCSD spin–spin coupling constants are also consistent with the changes in these same bonds. In particular, 1xJ(P–Cl) in H2XP:ClF complexes becomes 1J(P–Cl) in the ternary complexes with chlorine-transferred halogen bonds. A plot of these coupling constants shows a change in the curvature of the trendline as chlorine-shared halogen bonds in H2XP:ClF:ClH become chlorine-transferred halogen bonds in H2XP:ClF:ClF. 1xJ(F–Cl) coupling constants also reflect changes in the nature of F⋯Cl halogen bonds.

scholarly journals Hydrogen bonds and halogen bonds in complexes of carbones L→C←L as electron donors to HF and ClF, for L = CO, N2, HNC, PH3, and SH2

2020 ◽  
Vol 22 (28) ◽  
pp. 15966-15975
Author(s):  
Janet E. Del Bene ◽  
Ibon Alkorta ◽  
José Elguero
Keyword(s):  
Hydrogen Bonds ◽  
Electron Donor ◽  
Binding Energies ◽  
Electron Donors ◽  
Coupling Constants ◽  
Spin Coupling ◽  
Halogen Bonds ◽  
Spin Coupling Constants ◽  
Spin Spin Coupling

MP2 and EOM-CCSD calculations have been carried out to determine the structures, binding energies, and spin-spin coupling constants of carbone complexes L→C←L with the carbone the electron donor to HF or ClF, for L = CO, N2, HNC, PH3, and SH2.

Sign in / Sign up

Export Citation Format

Share Document